EP0288375A1 - Procédé d'usinage des métaux en présence de fluides fonctionnels aqueux renfermant des additifs extrême pression - Google Patents
Procédé d'usinage des métaux en présence de fluides fonctionnels aqueux renfermant des additifs extrême pression Download PDFInfo
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- EP0288375A1 EP0288375A1 EP88400945A EP88400945A EP0288375A1 EP 0288375 A1 EP0288375 A1 EP 0288375A1 EP 88400945 A EP88400945 A EP 88400945A EP 88400945 A EP88400945 A EP 88400945A EP 0288375 A1 EP0288375 A1 EP 0288375A1
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- water
- aqueous functional
- additive
- aqueous
- soluble salt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/72—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing sulfur, selenium or tellurium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/28—Polyoxyalkylenes of alkylene oxides containing 2 carbon atoms only
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/30—Polyoxyalkylenes of alkylene oxides containing 3 carbon atoms only
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/241—Manufacturing joint-less pipes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/242—Hot working
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/243—Cold working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- the present invention relates to extreme pressure additives for aqueous functional fluids as well as functional fluids and concentrated aqueous compositions containing said additives.
- aqueous functional fluids Water with high specific heat, heat of vaporization and thermal conductivity is the best coolant. As it is at the same time the most economical and the most harmless vis-à-vis the environment, the use of aqueous functional fluids is becoming widespread. These aqueous functional fluids can be true aqueous solutions of different additives in water, called synthetic fluids, or microemulsions, called semi-synthetic fluids. Semi-synthetic fluids also contain water, mineral oils and surfactants.
- the sulfur products used as extreme pressure additives in lubricants based on mineral oils or emulsions are dialkyl polysulfides, sulfur polyisobutenes and esters of sulfurized fatty acids. All of these products have little or no water solubility.
- the formulations of these products require the addition of large quantities of bactericidal agents commonly used in emulsions but generally excluded from functional fluids.
- the extreme pressure additive for aqueous functional fluids consists of a water-soluble salt, 3,3′-dithiodipropionic acid (SCH2CH2CO2H) 2 or 3-mercaptopropionic acid disulfide.
- water-soluble salt is meant here any salt, mineral or organic, whose solubility in water at room temperature is at least 0.01%, the preferred salts being those whose solubility is at least 0.1% .
- 3-Mercaptopropionic acid disulfide is a known product which is easily prepared by oxidation of 3-mercaptopropionic acid by sulfur or a conventional oxidant such as hydrogen peroxide.
- the salts used according to the invention are obtained in a manner known per se by neutralization in an aqueous medium of the disulfide with an organic or inorganic base.
- an organic or inorganic base for this purpose, it is possible to use the oxides, hydroxides or carbonates of alkali metals or alkaline earth metals, ammonia or nitrogenous organic bases.
- organic nitrogenous bases leading to water-soluble salts there may be mentioned more particularly mono-, di- or trialkylamines and cycloalkylamines containing not more than 8 total carbon atoms (preferably from 1 to 6), as well as substituted alkylamines on at least one alkyl radical by one or more hydrophilic groups such as OH, COOH or poly (oxyethylene and / or propylene).
- mono-, di- or triethanolamines are used.
- aqueous solutions of the salts according to the invention are perfectly stable and are easily stored without the release of hydrogen sulphide even in a neutral medium at pH7.
- the inorganic base salts can also be isolated in the form of crystals.
- the salts according to the invention are incorporated into aqueous fluids in a concentration by weight ranging from 0.01 to 20%, and preferably from 0.1 to 10%.
- additives for aqueous fluids can be used alone but in general they are used in admixture with other usual additives for aqueous fluids.
- additives with anti-wear, anti-rust and anti-foam effect can be mentioned.
- aqueous functional fluids are synthetic or semi-synthetic in nature. Synthetic fluids are true aqueous solutions of different additives in water. Their lubricating effect can be improved by adding polyglycols such as polyethylene glycols, polypropylene glycols or their copolymers.
- Semi-synthetic fluids are microemulsions containing a mineral or synthetic oil and a surfactant.
- the oil improves the lubricating properties of the aqueous fluid.
- 3-mercaptopropionic acid disulfide salts are perfectly stable in an aqueous medium, it is possible to store them in the form of concentrated mixtures of additives which are diluted at the time of use.
- These concentrates contain between 1 and 50% by weight and preferably between 15 and 35% of disulfide of 3-mercaptopropionic acid, as well as, possibly, other usual additives such as anti-rust, anti-wear and anti additives. foam, surfactants tifs, polyglycols or mineral or synthetic oils.
- a 4-ball machine test comprises 10 successive tests during which a ball trapped in a mandrel rotates for 10 seconds on three balls held in a cup filled with the extreme pressure fluid to be tested. By a system of weights, the three balls press more and more strongly, from one test to the next, on the rotating ball (the weights are in geometric progression).
- GRIPPAGE (or last charge before seizure) is the charge from which the curve A moves away from an ideal line, called the HERTZ line. It corresponds to the presence of a few solder points in contact between the balls. The diameter of imprint or wear suddenly increases.
- WELDING (or welding load) is the load from which the 4 balls are welded together preventing the rotation of the upper ball on the other three.
- CMH (or maximum load of HERTZ) is a dimensionless coefficient based on the measurement of footprints formed by the upper ball on the three fixed lower balls. The higher this coefficient, without any real physical significance, the more the oil tested is considered good from the point of view of extreme pressure.
- This salt was incorporated at various concentrations in a synthetic fluid (aqueous solution) containing 5% of ELF XT 6720 or in a semi-synthetic fluid (microemulsion) containing 5% of ELF TX 6760.
- ELF XT 6720 and 6760 are concentrates of commercial additives which bring good lubricating properties to water (oiliness, anti-corrosion properties, etc.).
- XT 6720 is a water-soluble concentrate containing polyglycols.
- XT 6760 is a microemulsifiable concentrate containing in particular a surfactant and a mineral oil.
- the diethanolamine salt of 3-mercaptopropionic acid disulfide (DEA DAM 3 P) was used.
- a polyethylene glycol of average molar mass 400 (denoted PEG 400) was incorporated into the aqueous phase to improve its lubricating properties.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
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Abstract
Description
- La présente invention concerne des additifs extrême pression pour fluides fonctionnels aqueux ainsi que des fluides fonctionnels et des compositions aqueuses concentrées renfermant lesdits additifs.
- Beaucoup d'opérations industrielles, comme par exemple l'usinage des métaux tel que le percage, le meulage, le tournage, le fraisage, le laminage, le tréfilage ou l'emboutissage, nécessitent la présence de fluides dits fonctionnels.
- Le rôle de ces fluides est de diminuer les efforts de coupe, refroidir la pièce pour obtenir de bonnes caractéristiques dimensionnelles, éliminer les copeaux de la zone de coupe, donner un bon fini de surface à la pièce et accroître la durée de vie de l'outil.
- L'eau dont la chaleur spécifique, la chaleur de vaporisation et la conductibilité thermique sont élevées est le meilleur agent de refroidissement. Comme il est en même temps le plus économique et le plus inoffensif vis-à-vis de l'environnement, l'emploi de fluides fonctionnels aqueux se généralise. Ces fluides fonctionnels aqueux peuvent être des solutions aqueuses vraies de différents additifs dans l'eau, appelés fluides synthétiques ou bien des microémulsions, appelées fluides semi-synthétiques. Les fluides semi-synthétiques renferment en plus de l'eau, des huiles minérales et des tensioactifs.
- Pour les opérations d'usinage à haute pression, l'utilisation de fluides fonctionnels aqueux n'a pas encore trouvé de solution satisfaisante.
- Pour ces opérations, la friction entre surfaces métalliques devient très importante et il est nécessaire d'utiliser des additifs extrême pression. Le rôle de ces additifs consiste à former une couche de protection sur les surfaces métalliques. Cette couche ou film protecteur évite le grippage ou pire la soudure de la pièce travaillée avec l'outil de travail.
- Les plus couramment utilisés parmi ces additifs extrême pression, puisque les plus efficaces, sont des additifs soufrés. Le contact des surfaces métalliques chaudes provoque la décomposition des produits soufrés et la formation d'une couche, continuellement renouvelée, de sulfures métalliques de protection.
- Les produits soufrés employés comme additifs extrême pression dans les lubrifiants à base d'huiles minérales ou d'émulsions sont des polysulfures de dialkyle, les polyisobutènes soufrés et les esters d'acides gras sulfurés. Tous ces produits sont peu ou pas solubles dans l'eau.
- On a essayé de pallier cet inconvénient par l'emploi d'additifs extrême pression solubles dans l'eau.
- L'article de R.W. MOULD de la British Petroleum Co Ltd. (Journal of the Americain Society of Lubrication Engineers 33(6)291-298 (1977)) étudie l'efficacité d'un certain nombre de produits halogénés ou soufrés hydrosolubles comme additifs extrême pression pour fluides aqueux. Les produits halogénés, en général chlorés, sont très peu efficaces. Les produits soufrés étudiés, comme les sels de sodium de l'acide thiosalicylique, de l'acide 2-mercaptopropionique, 2-2′-dithiodibenzoïque, 2,2′-dithiodipropionique, le disodium-L-cystine et le disodiumdithiodiglycolate sont peu stables et favorisent les développements bactériens et la libération d'hydrogène sulfuré.
- Les formulations de ces produits requièrent pour être stabilisées l'addition de quantités importantes d'agents bactéricides couramment utilisés dans les émulsions mais généralement exclus des fluides fonctionnels.
- Le brevet américain 4.250.046 décrit l'utilisation du diethanoldisulfure comme additif extrême pression. Ce produit est cependant incompatible avec de nombreux additifs couramment utilisés dans la formulation de fluides semi synthétiques.
- Nous avons trouvé maintenant un additif extrême pression, soluble dans l'eau, efficace et stable.
- L'additif extrême pression pour fluides fonctionnels aqueux selon l'invention consiste en un sel hydrosoluble, de l'acide 3,3′-dithiodipropionique (SCH₂CH₂CO₂H)₂ ou disulfure de l'acide 3-mercaptopropionique.
- Par sel hydrosoluble on entend ici tout sel, minéral ou organique, dont la solubilité dans l'eau à température ambiante est d'au moins 0,01 %, les sels préférés étant ceux dont la solubilité est d'au moins 0,1 %.
- Le disulfure de l'acide 3-mercaptopropionique est un produit connu qui se prépare facilement par oxydation de l'acide 3-mercaptopropionique par le soufre ou un oxydant classique tel que l'eau oxygénée.
- Les sels utilisés selon l'invention s'obtiennent de façon connue en soi par neutralisation en milieu aqueux du disulfure avec une base organique ou inorganique. A cet effet, on peut utiliser les oxydes, hydroxydes ou carbonates des métaux alcalins ou de métaux alcalinoterreux, l'ammoniaque ou les bases organiques azotées. Comme bases organiques azotées conduisant à des sels hydrosolubles, on peut citer plus particùlièrement les mono-, di- ou trialkylamines et cycloalkylamines ne contenant pas plus de 8 atomes de carbone au total (de préférence de 1 à 6), ainsi que les alkylamines substituées sur au moins un radical alkyle par un ou plusieurs groupements hydrophiles tels que OH, COOH ou poly(oxyéthylène et/ou propylène). On utilise avantageusement les mono-, di- ou triéthanolamines.
- Les solutions aqueuses des sels selon l'invention sont parfaitement stables et se conservent aisément sans dégagement d'hydrogène sulfuré même en milieu neutre à pH7. Si on le désire, on peut aussi isoler les sels de bases inorganiques sous forme de cristaux.
- Les sels selon l'invention sont incorporés aux fluides aqueux en concentration pondérale allant de 0,01 à 20 %, et de préférence de 0,1 à 10 %.
- Ils peuvent être utilisés seuls mais en général on les utilise en mélange avec d'autres additifs usuels des fluides aqueux. Parmi ces additifs on peut mentionner les additifs à effet anti-usure, anti-rouille et anti-mousse.
- Les fluides fonctionnels aqueux sont de nature synthétique ou semi synthétique. Les fluides synthétiques sont des solutions aqueuses vraies de différents additifs dans l'eau. Leur effet lubrifiant peut être amélioré par addition de polyglycols tels que les polyéthylèneglycols, les polypropylèneglycols ou leurs copolymères.
- Les fluides semi-synthétiques sont des microémulsions renfermant une huile minérale ou synthétique et un tensioactif. L'huile améliore les propriétés lubrifiantes du fluide aqueux.
- Comme les sels du disulfure de l'acide 3-mercaptopropionique sont parfaitement stables en milieu aqueux, il est possible de les stocker sous forme de mélanges concentrés d'additifs que l'on dilue au moment de l'utilisation. Ces concentrés renferment entre 1 et 50 % en poids et de préférence entre 15 et 35 % de disulfure de l'acide 3-mercaptopropionique, ainsi que, éventuellement, d'autres additifs usuels comme les additifs anti-rouille, anti-usure et anti-mousse, les agents tensioac tifs, des polyglycols ou des huiles minérales ou synthétiques.
- L'efficacité des additifs selon l'invention est évaluée par des essais sur machine à 4 billes par le test dit en 10 points (norme ASTM D 2783).
- Un test machine 4 billes comporte 10 essais successifs au cours desquels une bille emprisonnée dans un mandrin tourne pendant 10 secondes sur trois billes maintenues dans une coupelle remplie du fluide extrême pression à tester. Par un système de poids, les trois billes appuient de plus en plus fortement, d'un essai au suivant, sur la bille tournante (les poids sont en progression géométrique).
- Au cours de chacun des essais le diamètre des empreintes observées sur les trois billes fixes est mesuré et on trace une courbe A en échelle logarithmique donnant le diamètre d'empreinte en fonction de la charge appliquée.
- GRIPPAGE (ou dernière charge avant grippage) est la charge à partir de laquelle la courbe A s'éloigne d'une ligne idéale, appelée ligne de HERTZ. Elle correspond à la présence de quelques points de soudure au contact entre les billes. Le diamètre d'empreinte ou d'usure croît subitement.
- SOUDURE (ou charge de soudure) est la charge à partir de laquelle les 4 billes sont soudées entre elles en empêchant la rotation de la bille supérieure sur les trois autres.
- CMH (ou charge maximale de HERTZ) est un coefficient sans dimension basé sur la mesure d'empreintes que forme la bille supérieure sur les trois billes inférieures fixes. Plus ce coefficient, sans vraie signification physique, est élevée, plus l'huile testée est considérée comme bonne du point de vue de l'extrême pression.
- Les exemples 1 à 7 suivants illustrent l'invention sans la limiter. Les sels utilisés ont été obtenus et mis en oeuvre sous forme de solutions aqueuses préparées comme dans l'exemple type suivant :
- Dans un réacteur agité, on dissout 1050 g (5 moles) du disulfure de l'acide 3-mercaptopropionique dans 1590 ml d'eau, puis on ajoute lentement 610 g (10 moles) de monoéthanolamine pure. La solution obtenue qui contient environ 50 % de 3,3′-dithiodipropionate de di(monoéthanolamine) peut être utilisée telle quelle ou sous forme diluée.
-
- Ce sel a été incorporé à diverses concentrations dans un fluide synthétique (solution aqueuse) renfermant 5 % de ELF XT 6720 ou dans un fluide semi synthétique (microémulsion) renfermant 5 % de ELF TX 6760.
- Les ELF XT 6720 et 6760 sont des concentrés d'additifs commerciaux amenant à l'eau de bonnes propriétés lubrifiantes (onctuosité, propriétés anticorrosion ...).
- Le XT 6720 est un concentré soluble dans l'eau, renfermant des polyglycols.
-
- L'addition de DEA DAM 3 P dans une formulation commerciale classique permet d'améliorer considérablement les propriétés extrême pression de celle-ci. (CMH passant de 32 ou 34 à 77-78).
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Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88400945T ATE75249T1 (de) | 1987-04-24 | 1988-04-19 | Verfahren zur metallbearbeitung mit hilfe von waessrigen funktionnellen fluessigkeiten, die additive mit ep-eigenschaften enthalten. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8705778 | 1987-04-24 | ||
FR8705778A FR2614312B1 (fr) | 1987-04-24 | 1987-04-24 | Additifs hydrosolubles a effet extreme pression pour fluides fonctionnels aqueux, fluides fonctionnels et compositions aqueuses concentrees renfermant lesdits additifs. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0288375A1 true EP0288375A1 (fr) | 1988-10-26 |
EP0288375B1 EP0288375B1 (fr) | 1992-04-22 |
Family
ID=9350420
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88400945A Expired - Lifetime EP0288375B1 (fr) | 1987-04-24 | 1988-04-19 | Procédé d'usinage des métaux en présence de fluides fonctionnels aqueux renfermant des additifs extrême pression |
Country Status (22)
Country | Link |
---|---|
US (1) | US4880552A (fr) |
EP (1) | EP0288375B1 (fr) |
JP (1) | JPS63284294A (fr) |
KR (1) | KR900005104B1 (fr) |
CN (1) | CN1011595B (fr) |
AR (1) | AR245191A1 (fr) |
AT (1) | ATE75249T1 (fr) |
AU (1) | AU600122B2 (fr) |
BR (1) | BR8801867A (fr) |
CA (1) | CA1337075C (fr) |
DE (1) | DE3870303D1 (fr) |
DK (1) | DK173260B1 (fr) |
ES (1) | ES2006638A6 (fr) |
FI (1) | FI95479C (fr) |
FR (1) | FR2614312B1 (fr) |
GR (1) | GR3005146T3 (fr) |
IE (1) | IE61691B1 (fr) |
IL (1) | IL85779A (fr) |
IN (1) | IN171118B (fr) |
NO (1) | NO169179C (fr) |
PT (1) | PT87320B (fr) |
ZA (1) | ZA882823B (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1156100A1 (fr) * | 2000-05-19 | 2001-11-21 | Atofina | Lubrifiant aqueux multifoncitionnel à base d'acide dithiodiglycolique |
WO2009156621A1 (fr) * | 2008-06-27 | 2009-12-30 | Ifp | Solution absorbante contenant un inhibiteur de dégradation soufré à groupement carboxyle et méthode pour limiter la dégradation d'une solution absorbante |
WO2009156620A1 (fr) * | 2008-06-27 | 2009-12-30 | Ifp | Solution absorbante contenant un inhibiteur de dégradation multisoufré à groupement carboxyle et méthode pour limiter la dégradation d'une solution absorbante |
CN109913309A (zh) * | 2013-05-31 | 2019-06-21 | Ntn株式会社 | 水溶性切削或磨削液 |
WO2023275307A1 (fr) * | 2021-07-01 | 2023-01-05 | Totalenergies Onetech | Composition lubrifiante aqueuse pour le travail des métaux |
FR3124800A1 (fr) * | 2021-07-01 | 2023-01-06 | Totalenergies Marketing Services | Composition lubrifiante aqueuse pour le travail des métaux |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1998008919A2 (fr) * | 1996-08-30 | 1998-03-05 | Solutia Inc. | Nouveaux fluides hydrosolubles d'usinage de metaux |
JP3359267B2 (ja) * | 1997-09-02 | 2002-12-24 | タイユ株式会社 | 切削加工方法 |
FR2832160B1 (fr) * | 2001-11-15 | 2005-01-14 | Atofina | PROCEDE DE TRAVAIL OU MISE EN FORME DES METAUX EN PRESENCE DE LUBRIFIANTS AQUEUX A BASE D'ACIDE METHANESULFONIQUE (AMS) ou D'UN SEL HYDROSOLUBLE D'AMS |
DE10256639A1 (de) * | 2002-12-03 | 2004-06-24 | Thyssenkrupp Stahl Ag | Schmierstoffbeschichtetes Metallblech mit verbesserten Umformeigenschaften |
JP4981240B2 (ja) * | 2003-02-05 | 2012-07-18 | 出光興産株式会社 | 潤滑油用及び燃料油用添加剤、並びに潤滑油組成物及び燃料油組成物 |
US7714049B2 (en) | 2006-08-14 | 2010-05-11 | The Yokohama Rubber Co., Ltd. | Compounding agent for rubber vulcanization containing amine salt compound of carboxylic group-containing disulfide, method for producing the same, rubber composition containing the same and pneumatic tire using the same as rubber for belt coat and/or belt edge cush |
JP6009378B2 (ja) * | 2013-03-06 | 2016-10-19 | 出光興産株式会社 | 水溶性金属加工油剤および金属加工用クーラント |
JP6283552B2 (ja) * | 2014-03-28 | 2018-02-21 | 出光興産株式会社 | 水溶性金属加工油および金属加工用クーラント |
CN107760433A (zh) * | 2017-12-05 | 2018-03-06 | 苏州市宽道模具机械有限公司 | 一种金属水基切削液及其制备方法 |
CN108485773A (zh) * | 2018-05-30 | 2018-09-04 | 海宁贵德孚精密机械有限公司 | 一种电机轴承润滑脂及其制备方法 |
CN113322121A (zh) * | 2021-05-28 | 2021-08-31 | 上海尤希路化学工业有限公司 | 新能源汽车用SiC第三代功率半导体晶片切割液 |
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DE2642666A1 (de) * | 1975-09-22 | 1977-03-24 | M & T Chemicals Inc | Verfahren und zusammensetzung zur herstellung einer galvanischen abscheidung |
DE3014654A1 (de) * | 1979-04-18 | 1980-11-06 | Asahi Chemical Co | Faerbeverfahren |
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FR954723A (fr) * | 1946-10-28 | 1950-01-05 | ||
US2649416A (en) * | 1949-03-03 | 1953-08-18 | Socony Vacuum Oil Co Inc | Lubricating oil containing a monoester of a thiodiacetic acid |
NL75960C (fr) * | 1951-04-23 | |||
US2794049A (en) * | 1953-11-17 | 1957-05-28 | Universal Oil Prod Co | Dithia-dioxo-hydrocarbons |
US2815368A (en) * | 1954-03-17 | 1957-12-03 | Exxon Research Engineering Co | Complex ester synthetic lubricants |
US2845390A (en) * | 1956-02-23 | 1958-07-29 | Cities Service Res & Dev Co | Lubricating composition |
NL239215A (fr) * | 1958-05-19 | |||
US3278434A (en) * | 1963-07-30 | 1966-10-11 | Exxon Research Engineering Co | Lubricant compositions containing thiodicarboxylic acid esters |
US4036709A (en) * | 1975-09-22 | 1977-07-19 | M & T Chemicals Inc. | Electroplating nickel, cobalt, nickel-cobalt alloys and binary or ternary alloys of nickel, cobalt and iron |
JPS53134049A (en) * | 1977-04-11 | 1978-11-22 | Sankyo Yuki Gosei Kk | Stabilization of synthetic resin |
US4248723A (en) * | 1977-06-23 | 1981-02-03 | Ciba-Geigy Corporation | Acetal derivatives as extreme pressure additives for lubricants |
US4250046A (en) * | 1979-03-05 | 1981-02-10 | Pennwalt Corporation | Diethanol disulfide as an extreme pressure and anti-wear additive in water soluble metalworking fluids |
DE3223973A1 (de) * | 1982-06-26 | 1983-12-29 | Degussa Ag, 6000 Frankfurt | Verfahren zur herstellung von ss-mercaptopropionsaeurederivaten |
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- 1987-04-24 FR FR8705778A patent/FR2614312B1/fr not_active Expired - Fee Related
-
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- 1988-03-18 IL IL85779A patent/IL85779A/xx not_active IP Right Cessation
- 1988-04-14 NO NO881617A patent/NO169179C/no not_active IP Right Cessation
- 1988-04-19 EP EP88400945A patent/EP0288375B1/fr not_active Expired - Lifetime
- 1988-04-19 AT AT88400945T patent/ATE75249T1/de not_active IP Right Cessation
- 1988-04-19 DE DE8888400945T patent/DE3870303D1/de not_active Expired - Fee Related
- 1988-04-20 BR BR8801867A patent/BR8801867A/pt not_active IP Right Cessation
- 1988-04-21 ZA ZA882823A patent/ZA882823B/xx unknown
- 1988-04-21 ES ES8801234A patent/ES2006638A6/es not_active Expired
- 1988-04-21 US US07/184,425 patent/US4880552A/en not_active Expired - Lifetime
- 1988-04-21 IN IN253/MAS/88A patent/IN171118B/en unknown
- 1988-04-22 CA CA000564816A patent/CA1337075C/fr not_active Expired - Fee Related
- 1988-04-22 FI FI881913A patent/FI95479C/fi not_active IP Right Cessation
- 1988-04-22 AU AU15110/88A patent/AU600122B2/en not_active Ceased
- 1988-04-22 DK DK198802197A patent/DK173260B1/da not_active IP Right Cessation
- 1988-04-22 PT PT87320A patent/PT87320B/pt not_active IP Right Cessation
- 1988-04-22 IE IE122488A patent/IE61691B1/en not_active IP Right Cessation
- 1988-04-22 AR AR88310635A patent/AR245191A1/es active
- 1988-04-23 KR KR1019880004641A patent/KR900005104B1/ko not_active IP Right Cessation
- 1988-04-23 CN CN88102384A patent/CN1011595B/zh not_active Expired
- 1988-04-25 JP JP63102336A patent/JPS63284294A/ja active Granted
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1992
- 1992-07-13 GR GR920401489T patent/GR3005146T3/el unknown
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1156100A1 (fr) * | 2000-05-19 | 2001-11-21 | Atofina | Lubrifiant aqueux multifoncitionnel à base d'acide dithiodiglycolique |
FR2809117A1 (fr) * | 2000-05-19 | 2001-11-23 | Atofina | Lubrifiant aqueux multifonctionnel a base d'acide dithiodiglycolique |
US6355604B2 (en) | 2000-05-19 | 2002-03-12 | Atofina | Multifunctional aqueous lubricant based on dithiodiglycolic acid |
WO2009156621A1 (fr) * | 2008-06-27 | 2009-12-30 | Ifp | Solution absorbante contenant un inhibiteur de dégradation soufré à groupement carboxyle et méthode pour limiter la dégradation d'une solution absorbante |
WO2009156620A1 (fr) * | 2008-06-27 | 2009-12-30 | Ifp | Solution absorbante contenant un inhibiteur de dégradation multisoufré à groupement carboxyle et méthode pour limiter la dégradation d'une solution absorbante |
FR2933006A1 (fr) * | 2008-06-27 | 2010-01-01 | Inst Francais Du Petrole | Solution absorbante contenant un inhibiteur de degradation soufre a groupement carboxyle et methode pour limiter la degradation d'une solution absorbante |
FR2933005A1 (fr) * | 2008-06-27 | 2010-01-01 | Inst Francais Du Petrole | Solution absorbante contenant un inhibiteur de degradation multisoufre a groupement carboxyle et methode pour limiter la degradation d'une solution absorbante |
CN109913309A (zh) * | 2013-05-31 | 2019-06-21 | Ntn株式会社 | 水溶性切削或磨削液 |
WO2023275307A1 (fr) * | 2021-07-01 | 2023-01-05 | Totalenergies Onetech | Composition lubrifiante aqueuse pour le travail des métaux |
FR3124802A1 (fr) * | 2021-07-01 | 2023-01-06 | Totalenergies Marketing Services | Composition lubrifiante aqueuse pour le travail des métaux |
FR3124800A1 (fr) * | 2021-07-01 | 2023-01-06 | Totalenergies Marketing Services | Composition lubrifiante aqueuse pour le travail des métaux |
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